DE1063379B - Process for the production of linear polymerisation or polycondensation products with improved heat resistance and reduced electrostatic charge - Google Patents

Description

GERMAN

The invention relates to a process for the production of linear polymerization or polycondensation products with improved heat resistance and reduced electrostatic charge.

It is known that the heat resistance of linear high polymers can be achieved by at the production of which adds small amounts of an N-aminoalkylmorpholine to the starting materials, so that these added compound acts as a stabilizer. This means that when the high polymer is heated, especially of the polyamide, the viscosity at the melting point remains unchanged. It is for the same purpose already described in the production of linear condensation products from diamines and dicarboxylic acids add a small amount of zinc acetate and copper stearate to these starting materials. It was also used to stabilize linear polycarboxamides these polycondensates a small amount of a mixture of a phosphorus compound and added to an alkali halide. ao

The elimination of the unpleasant electrostatic charge of synthetic linear high polymers, which occurs when processing into threads or fibers, does not yet set for some types of fiber The problem has been solved satisfactorily. It is known that fibers made from synthetic, linear high polymers a large electrostatic charge that arises during their manufacturing or spinning process. It is already known that the threads with solutions of low molecular weight condensation products of a secondary act to submit. Likewise, the tendency of the fibers to become electrostatically charged is no longer new. by treatment with salt solutions formed from aliphatic oxyacids and alkylolamines to reduce. Solutions that are suitable for synthetic treatment have also been used Staple fibers are suitable and are composed of an alkylolamine salt of a fatty acid on the one hand and the alkylolamine salt of a aliphatic dicarboxylic acid on the other hand. It is also known to use triethanolamine alone or to use the salts of triethanolamine with sebacic acid or adipic acid as antistatic agents for polyamide threads. However, the compounds listed here often have the disadvantage that the substances applied cause a yellowing of the threads and, furthermore, that also the use of the threads equipment used are attacked to a greater or lesser extent. Often there is the disadvantage of so far Suggested compounds also in that they are water-soluble and do not remain in the end product, So be washed out.

It has been found that there is a refinement of synthetic, linear polymers or polycondensates, which result in an improvement in the Wärmebe process for production
of linear polymerization or

Polycondensation products
with improved heat resistance and reduced electrostatic charge

Applicant:

United Glanzstoff-Fabriken AG,
Wuppertal-Elberfeld, Glanzstoff House

Dr. Rudolf Lotz, Obernburg / M.,
and Gerhard Wick, Erlenbach / M.,
have been named as inventors

Stability of the linear high polymers and a simultaneous reduction in the electrostatic charge of the threads and fibers formed from the high polymers is achieved when either the monomeric starting materials in the presence of small amounts of 0.05 to 2 ° / ₀ , based on the monomers, a aromatic distannane or digermanane compound of the general formula

R., R

IT R

wherein A is either a tin or germanium atom and R is an optionally halogenated, alkylated or aralkylated one Denotes phenyl group or a naphthyl group or a cyclohexyl group, polymerized or polycondensed or that the linear synthetic polymers with small amounts of one of these distannan- or Digermanan compounds treated. As compounds which are used according to the invention, The following can be named: Hexaphenyldistannan, Hexacyclohexyldistannan, Hexaphenyldigermanan, Hexacyclohexyldigermanan, hexa-p-toluyldistannan, Hexanaphthyl distannane. Synthetic compounds are suitable for treatment with these compounds linear high polymers such as polyacrylonitrile, polyamides formed from either caprolactam or hexamethylene diamine adipate or polyethylene terephthalate. According to the invention, the above-mentioned distannan- or Digermananverbindungen the monomers, so the

909 607/440

Claims (1)

3 4 ^ .crylsäurenitril, the Caprolactam, the Hexamethy- Example 3 enediamine adipate or the terephthalic acid diglycol ester, 2000 g of hexamethylenediamine adipate are mixed with 2 g ; ugesetzt, and the polymerization or polycondene hexacyclohexyldistannane added and at 212 ° C and iation is carried out according to standard procedures. It is about 18 atmospheres in the autoclave for 4 hours poly- On the other hand, however, it is also possible for the compounds 5 to be condensed. An increase in temperature follows len finished polymers or polycondensates at 250 ° C for 2 more hours, during the water to stay with. In any case, it is achieved that the steam pressure is slowly released. After a inear high polymers both in terms of heat- a further 3 hours of heating to 270 ° C below normal stabilization as well as with regard to the electrostatic pressure, the approach is finished polycondensed. The in effect receives remuneration. The above-mentioned polycondensate is pure white, and that from it Dindungen are characterized, among other things, threads produced thereby show a relatively low electrical lus that they are insoluble in water, so not out-static charge, expressed by their electrical can be washed. Resistance with 10 · 10 ⁹ ohms. Using germanium compounds as a counter-attempt was the same approach, however Catalysts in the production of polyethylene-15 without hexacyclohexyldistannane, among the same terephthalate polycondensed by polycondensation of diglycol, temperature and pressure conditions, terephthalate is known. The threads produced from them show a very high level of inorganic substances Germanium compounds, e.g. B. germanium oxides or electrostatic charge, whereby the electrical resistance xietallic germanium, used. The additional amounts stood with over 10,000 · 10 ⁹ ohms being measured. should be between 0.001 and 0.05 percent by weight (based on 20. based on terephthalic acid or its esters). This eispie Compounds are not suitable, a refinement in 1800 g polyacrylonitrile (K value approx. = 96) was in To bring about the sense of the present invention. You 8200 g of dimethylformamide with the addition of 10 g of hexa- Do not lead to any reduction in the electrostatic naphthyldistannan suspended and the approach in the usual way Charging. The purpose and effect of being heated to temperatures of about 110 ° C in the 25 way, so that Polycondensation of added germanium compounds, a clear spinning solution is created. The out of this spinning According to the known method, the threads obtained in the solution are in a ratio of 1: 6 not drawn with the addition of the process according to the invention. The measurement of the electrostatic charge comparable. gave a value of 1.3 · 10 ⁹ ohms. 30 As a counter-attempt, the same approach was used, however Example 1 without the addition of hexanaphthyl distannane, worked up. The measurement of the electrostatic charge on the threads To 226 g of caprolactam and 6 mole percent distilled gave a very high value of 10,000 · 10 ⁹ ohms. Water are 3000 mg ε-aminocaproic acid as a catalyst. . Sator and 230 mg of hexacyclohexyl distannane added, 35 example and the batch is heated according to a known method to 600 g of terephthalic acid diglycol ester with condensing temperatures until the 600 mg of zinc oxide-boron trioxide and 60 mg of the resulting polycondensate have become stringy. Hexa-p-toluyldistannane on polycondensing tempe- The polycondensate is pure white and is heated for the purpose of temperatures. A pure white polycondensate is obtained with no oligomers still adhering for 6 hours at 4 ° from a K value of about = 51. The water distilled from this polycondensate is extracted. The polycondensate is now melted using the melt-spinning process, and filaments are spun into threads using a conventional method showing a low level of electrostatic charge. The resulting threads are used to measure the electrical resistance of conductivity measurements by means of a megohmmeter 50 · 10 ⁹ ohms. carried out. Here, the electrical resistance 45. As a counter-experiment, the same approach was used for of the threads measured. It gives a value of making the polyethylene terephthalate used, 50 x 10 ⁹ ohms. however, the hexa-p-toluyldistannane is not part of the batch As a counter-test, the same approach, caprolactam, is added. The polycondensates obtained are but without the addition of hexacyclohexyl distannane, then according to the usual melt spinning process also heated to condensing temperatures. It processes 50 threads. These threads show an electro- the resulting polycondensate threads generate a static charge of over 10,000 · 10 ⁹ ohms. manufactured. It shows a very high electrostatic. . Charge that is greater than 1000 · 10 ⁹ ohms. Example 6 For 1000 g of polyethylene terephthalate (K value approx. = 52) Examples _{55 were (} j _en 200 mg of hexacyclohexyl digermanane added and 1000 g of a polyamide produced from caprolactam, the polyester melted in an inert gas stream and (K value approx. = 69) are combined with 1 g of hexacyclohexyl to form threads according to the usual melt spinning process. digermanan and so long in the inert gas stream. The electrostatic charge of the manufactured melted until the added connection threads gave a relatively low value, expressed in it dissolves. The result is a clear, stringy melt, 60 due to the measured resistance of 30 · 10 ⁹ ohms. from which threads are made according to the usual method. Counter-experiment: The same approach, but without addition will. The conductivity measurements with the megohm of Hexacyclohexyldigermanan were according to the usual meters showed a relatively low level of electrostatic build-up. The threads show one charge, expressed in an electrical resistance, high electrostatic charge of over 10,000 · 10 ⁹ ohms. of 3.0 x 10 ⁹ ohms. 6 ₅ As a counter-attempt, the same approach of the poly claim was made: amides, but without the addition of Hexacyclohexyldiger- process for the production of linear poly manan, melted and processed into threads. The merization or polycondensation products with electrostatic charge showed a value of over improved heat resistance and decreased 1000 x 10 ⁹ ohms. 7 ° electrostatic charge, characterized by • that either the monomeric starting materials in the presence of small amounts of 0.05 to 2 ⁰ _{I 0} , based on the monomers, of an aromatic or hydroaromatic distannane or digermanane compound of the general formula and R is an optionally halogenated, alkylated or aralkylated phenyl group or a naphthyl group or a cyclohexyl group, polymerized or polycondensed or that the lineaien synthetic polymers with small amounts of one of these distannane or digermanane compounds treated. where A is either a tin or a germanium atom xo Publications considered: U.S. Patent No. 2,578,660.